US20040178800A1 - Gas detector with modular detection and discharge source calibration - Google Patents

Gas detector with modular detection and discharge source calibration Download PDF

Info

Publication number
US20040178800A1
US20040178800A1 US10/387,011 US38701103A US2004178800A1 US 20040178800 A1 US20040178800 A1 US 20040178800A1 US 38701103 A US38701103 A US 38701103A US 2004178800 A1 US2004178800 A1 US 2004178800A1
Authority
US
United States
Prior art keywords
discharge
signal
collector
value
detector
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10/387,011
Other versions
US6842008B2 (en
Inventor
Stanley Stearns
Huamin Cai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Valco Instruments Co Inc
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US10/387,011 priority Critical patent/US6842008B2/en
Application filed by Individual filed Critical Individual
Priority to JP2005518597A priority patent/JP2007524803A/en
Priority to EP04737310A priority patent/EP1611437B8/en
Priority to DE602004024182T priority patent/DE602004024182D1/en
Priority to PCT/US2004/006981 priority patent/WO2004081523A2/en
Priority to CN2004800064690A priority patent/CN101027550B/en
Publication of US20040178800A1 publication Critical patent/US20040178800A1/en
Assigned to VALCO INSTRUMENTS CO., INC. reassignment VALCO INSTRUMENTS CO., INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CAI, HUAMIN
Application granted granted Critical
Publication of US6842008B2 publication Critical patent/US6842008B2/en
Assigned to VALCO INSTRUMENTS CO., L.P. reassignment VALCO INSTRUMENTS CO., L.P. CONVERSION OF CORPORATE ENTITY Assignors: VALCO INSTRUMENTS CO., INC.
Assigned to VALCO INSTRUMENTS COMPANY, INC. reassignment VALCO INSTRUMENTS COMPANY, INC. CONVERSION OF CORPORATE ENTITY Assignors: VALCO INSTRUMENTS COMPANY, L.P.
Adjusted expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/68Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
    • G01N27/70Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas and measuring current or voltage

Definitions

  • the present invention is directed to detectors for measuring concentrations of a gaseous sample, and more particularly directed toward a pulsed discharge detector that correlates collected data with the discharge and calibrates collected data to reduce effects of discharge noise.
  • detectors are used to quantify constituents of a sample gas.
  • Known detectors vary in how they make the sample detectable, arrange the necessary components of the detector, actually detect characteristics of the sample and process the detected data.
  • Pulsed discharge detectors ionize a discharge gas in a chamber to produce photons, introduce a sample gas to be tested and measure ionization currents of electrons produced from interaction of the photons with the sample gas.
  • the ionization source of the detector is an electrical discharge in a discharge gas.
  • the discharge gas may be a noble gas or a combination of noble gases.
  • a pulsed discharge detector may be provided with a sample input gas eluted from a gas chromatograph column or other suitable source.
  • the column effluent normally includes a carrier gas which is routinely input through the column at a specified flow rate.
  • the column elutes the various constituents in peaks of concentration in a specific timed sequence, dependent on volatility of the sample constituents.
  • the gas chromatograph column separates compounds but does not quantify the concentrations of the compounds.
  • Gas chromatograph detectors are connected downstream the column for quantitative analysis.
  • the gas chromatograph column can be used to separate compound types based upon the retention time. There may be any number of eluted peaks formed by the gas chromatograph column output to be quantified.
  • the ionization mechanism of a pulsed discharge detector is primarily photo-ionization wherein an electric discharge generates diatomic molecular emissions of photons.
  • the high-energy photons in turn ionize the sample compounds in the detector chamber.
  • the pulsed discharge detector uses helium as the discharge gas, the photon generation process includes the following steps:
  • He + ions combine with helium atoms, He, to form diatomic molecular ions, He 2 + .
  • step 3 a continuous photon emission arises from the molecular interaction—the transition of diatomic helium molecular ions to ground state helium. These photons have an energy level in the range of 13.5 ⁇ 17.5 eV, which can ionize almost all compounds, except helium itself. Other processes of molecular interaction may also affect the electrical discharge, such as helium atomic emission and helium meta-stable generation.
  • Pulsed discharge detectors possess favorable characteristics over other gas chromatograph detectors. First, sensitivity is higher. The minimum detectable limit of gases present in a sample using a regular pulsed discharge detector in helium ionization detector mode is about 10 times lower than the minimum detectable limit identifiable using a flame ionization detector. Pulsed discharge detectors are operable to determine concentrations at the parts-per-billion level. Second, pulsed discharge detectors offer selectivity in response. Pulsed discharge detectors have a universal response when helium is used as the discharge gas. When helium is doped with another noble gas as the discharge gas, pulsed discharge detectors may have a selective response. Third, pulsed discharge detectors have a uniform response factor. Within an organic group the response factor increases linearly with the carbon number of the sample. Fourth, the pulsed discharge detector system does not require use of radioactive material.
  • U.S. Pat. No. 5,394,091 teaches an ionization detector adapted for use in either helium ionization or electron capture mode.
  • the detector utilizes a helium flow through a detector cell or chamber.
  • the chamber has regions of spark discharge, sample introduction and sample detection.
  • the helium flow is the only flowing material in the immediate region of the spark.
  • a sample gas and/or carrier gas are injected and commingled with the helium gas downstream from the spark in the sample introduction region.
  • Two electrodes, of which one is bias detect the charged characteristics of the sample, the bias electrode at or upstream of the sample inlet and the other electrode downstream from the sample inlet.
  • An electrometer measures the difference between the resulting currents. These current measurements are recorded on a timed basis.
  • a base line current is formed as a result of impurities in the discharge or carrier gas.
  • U.S. Pat. No. 5,767,683 teaches a pulsed discharge detector having a bias voltage feedback system.
  • the feedback system compares output from an electrometer connected to the collector electrode with a reference current using a comparison circuit.
  • Output from the comparison circuit is input to a control circuit, which, in turn, outputs a bias voltage.
  • the bias voltage is applied to the first bias electrode such that the electron current flow within the detector chamber remains constant for all concentrations of input sample gas.
  • the instantaneous setting of the control circuit is used to form a second output.
  • the magnitude of this second output is proportional to the concentration of a selected sample gas within the electron capture detector chamber and is the response signal of the disclosed electron capture detector system.
  • Pulsed discharge detectors provide intermittent electrode discharges.
  • a typical discharge voltage is in the range of 300 to 400 volts.
  • a typical time interval between discharges is in a range of 100 microseconds to 800 microseconds.
  • Discharge noise can be reduced by a high quality pulser and a clean discharge electrode surface, but cannot be eliminated.
  • the present invention provides an improvement to the prior art by increasing sensitivity of the pulsed discharge detector by providing a device and method to measure ionization signals in the sample gas modularly at the time of the discharge event as opposed to a collected current, by a geometric configuration that enhances collection of signals and by providing a means of calibrating collected signals to account for discharge noise.
  • the present invention accordingly provides an improvement to the prior art by allowing longer pulse periods, thereby reducing power requirement of a pulsed discharge detector and providing relatively longer product life.
  • the reduced power requirements of the detector of the present invention makes the detector particularly useful as a portable detector.
  • a pulsed discharge detector includes a device and method for modular measurement of ionization signals from a sample.
  • the pulsed discharge detector includes a discharge source in a chamber, a collector spaced from the discharge source, a monitor connected to a discharge electrode, an electrometer connected to the collector, a calibrator and a sample and hold processor.
  • the discharge electrodes include a source electrode centrally located in relation to the discharge chamber wall.
  • the collector is centrally located in relation to the chamber wall.
  • Discharge signals are monitored for time and intensity. Collected signals are adjusted based on the discharge intensity. Collected signals are collected during a time window based on the discharge occurrence time. Detector output is predicated on collected signals coordinated with pulsed discharges.
  • the calibrator of the present invention adjusts the collected signals to reduce discharge noise.
  • the sample and hold processor accumulates selected adjusted signal values to quantify sample concentrations.
  • the objects of this invention are to provide, among other things, a pulsed discharge detector and method of operation that:
  • FIG. 1 is a cross-sectional view of a detector of the present invention, including a schematic depiction of components.
  • FIG. 2A is a graphical depiction of a monitored discharge signal overtime.
  • FIG. 2B is a graphical depiction of the collected signal overtime as in FIG. 2A.
  • FIG. 2C is a graphical depiction of the adjusted signal overtime as in FIG. 2A.
  • FIG. 2D is a graphical depiction of the output signal overtime as in FIG. 2A.
  • FIG. 2E is a graphical depiction of an output signal over time indicating concentration of sample compounds.
  • FIG. 3 is a cross-sectional view of an alternative embodiment incorporating the components of the present invention.
  • detector 10 of the present invention is depicted.
  • Detector 10 is typically integrated into an analytical system.
  • Devices such as a gas chromatograph column (not shown) are typically used upstream of detector 10 to provide a sample gas (not shown), and other devices, such as a computer with interpretation software (not shown), are used to receive, store, manipulate and report generated data.
  • a primary purpose of detector 10 is to determine the quantities of compounds in a sample gas.
  • Detector 10 includes closed chamber 12 within detector housing 11 .
  • chamber 12 is an elongated hollow space in housing 11 , oriented lengthwise along chamber axis 18 .
  • One end of chamber 12 is discharge end 14 and the other is collector end 16 .
  • An electrical discharge source 20 is located proximate discharge end 14 .
  • discharge source 20 includes source electrode 22 and receptor electrode 24 .
  • Source electrode 22 extends into chamber 12 proximate discharge end 14 of housing 11 .
  • Tip 42 of source electrode 22 is located at the central axis 18 of cylindrical chamber 12 .
  • source electrode 22 extends through discharge end 14 at the center of discharge end 14 and is arranged co-axially with the central axis 18 of chamber 12 .
  • Electrical source connection 21 is located outside housing 11 and provides an electrically conductive link of source electrode 22 to a power source (not shown).
  • Receptor electrode 24 is emplaced circumferentially in the wall of housing 11 , proximate tip 42 of source electrode 22 .
  • receptor electrode 24 extends circumferentially about cylindrical chamber 12 .
  • Electrical receptor connection 23 is located outside housing 11 and provides an electrically conductive link to receptor electrode 24 .
  • the configuration of tip 42 in relation to electrode 24 allows tip 42 to be equally distant from electrode 24 surfaces.
  • Collector 26 extends into chamber 12 proximate collector end 16 .
  • Collector tip 46 is located at the central axis 18 of cylindrical chamber 12 .
  • collector 26 extends through collector end 16 at the center of collector end 16 and is arranged co-axially with the central axis 18 of chamber 12 . Accordingly, collector 26 is equally distant from chamber wall 28 .
  • Electrical collector connection 25 is located outside housing 11 and provides an electrically conductive link to collector 26 .
  • source electrode 22 and collector 26 are each elongated members aligned along axis 18 .
  • Collector tip 46 is spaced from source electrode tip 42 .
  • Chamber 12 includes discharge region 70 , expansion region 72 and collection region 74 .
  • Each of discharge region 70 , expansion region 72 and collection region 74 have circular cross-sections.
  • the diameter of the collection region 74 is greater than the diameter of discharge region 70 .
  • the diameter of expansion region 72 increases from its interface with discharge region 70 to its interface with collection region 74 .
  • Discharge region 70 extends from end 14 of chamber 12 past tip 42 .
  • Collector region 74 extends from end 16 of chamber 12 past collector tip 46 .
  • a discharge gas inlet 34 is provided proximate discharge end 14 to allow the introduction of discharge gas 30 into chamber 12 at discharge region 70 .
  • Discharge gas 30 may be helium, other suitable discharge gases known in the art, or combinations thereof.
  • Discharge gas inlet 34 connects to a pressurized supply (not shown) of discharge gas 30 .
  • discharge gas inlet 34 opens into chamber 12 intermediate discharge end 14 and source electrode tip 42 .
  • a sample gas inlet 36 accesses chamber 12 , in expansion region 72 to provide for introduction of a sample gas 32 (not shown).
  • Sample gas inlet 36 is connected to a source of sample gas such as a gas chromatograph column (not shown).
  • sample gas 32 includes a carrier gas, typically helium, and a volume of a sample matter.
  • the detector identifies such sample matter in sample gas 32 as variations from the carrier gas.
  • Gas vent 38 is provided at the collector end 16 of chamber 12 .
  • gas vent 38 penetrates housing 11 in collector region 74 proximate collector end 16 intermediate collector tip 46 and collector end 16 .
  • the chamber 12 accordingly comprises a relatively narrow discharge region 70 with discharge gas inlet 36 , a conical expansion region 72 with a sample gas inlet 36 and a cylindrical collector region 74 with a gas vent 33 .
  • Collector region 74 is relatively wider than inlet region 70 .
  • Electrometer 60 is attached to electrical connection 25 , electrically linking electrometer 60 to collector 26 .
  • a bias voltage 66 is applied to electrical connection 25 thereby providing bias voltage 66 to collector 26 and to electrometer 60 .
  • Electrometer 60 is electrically connected to calibrator 62 .
  • Calibrator 62 is electrically connected to sample and hold processor 64 .
  • Electrical receptor connection 23 provides an electrically conductive link from receptor electrode 24 to monitor 50 , comprising frequency monitor 52 and intensity monitor 54 .
  • Frequency monitor 52 and intensity monitor 54 are each electrically connected to calibrator 62 and to sample and hold processor 64 .
  • discharge gas inlet 34 is connected to a discharge gas supply line (not shown)
  • sample gas inlet 36 is connected to a sample gas supply line (not shown)
  • gas vent 38 is connected to a gas vent line (not shown).
  • the lines and detector 10 create a sealed environment.
  • the system is then filled with a discharge gas 30 such as helium.
  • a steady flow of discharge gas 30 is introduced through discharge gas inlet 34 .
  • the discharge gas 30 flows into chamber 12 and passes through chamber 12 , exiting gas vent 38 . Since sample gas inlet 36 is filled and pressurized with sample gas 32 , the only available flow path for discharge gas 30 is through the length of chamber 12 and then gas vent 38 .
  • the only means for any substance to enter chamber 12 is through discharge gas inlet 34 and sample gas inlet 36 , and the only matter that enters chamber 12 is discharge gas 30 and sample gas 32 .
  • pulsed high voltage discharge 40 is applied to electrical connection 21 creating a spark discharge intermediate source electrode 22 and receptor electrode 24 .
  • the spacing of source electrode 22 and receptor electrode 24 and the voltage level are arranged to cause ionization of discharge gas 30 particles generating diatomic molecular emissions of photons (not shown).
  • the ionized discharge gas 30 particles are conveyed toward sample gas inlet 36 and in turn ionize compounds of sample gas 32 in expansion region 72 and collector region 74 .
  • Pulsed discharge 40 results in a discharge signal 80 at receptor electrode 24 .
  • FIG. 2A comprises a graphical representation of discharge signal 80 over time.
  • pulsed discharge 40 is designed to produce a clean, distinct and discharge signal 80 with each repetition of pulsed discharge 40 , variations in intensity occur. Such variations are commonly referred to as “noise.”
  • discharge signal 80 is transmitted to discharge monitor 50 , comprising both frequency monitor 52 and intensity monitor 54 .
  • Frequency monitor 52 identifies synchronizing frequency signal value 84 , including a discharge time and a discharge period, comprising the interval between pulsed discharges 40 .
  • Intensity monitor 54 identifies intensity signal value 86 at receptor electrode 24 for each pulsed discharge 40 .
  • Frequency signal value 84 and intensity signal value 86 may be individually or collectively transmitted to calibrator 62 and sample and hold processor 64 .
  • Bias voltage 66 is applied to collector 26 through electrical connection 25 . Such bias voltage 66 enhances reception of charged sample gas ions at collector tip 46 . Bias voltage 66 may be positive or negative depending on the design of the detector. The amount of voltage used depends on the size of the detector.
  • Collected signal 90 is quantified by electrometer 60 .
  • Bias voltage 66 provides a measurement reference point. Bias voltage 66 variations create noise in collected signal 90 . Applying bias voltage 66 directly to input lead 61 of electrometer 60 , where electrical connection 25 connects with electrometer 60 , minimizes such noise. Electrometer 60 produces collected signal value 92 from collected signal 90 and bias voltage 66 .
  • intensity of collected signal value 92 over time is depicted. Collected signal value 92 is transmitted to calibrator 62 . Calibrator 62 adjusts collected signal value 92 based on intensity signal value 86 , producing adjusted signal value 94 . Such adjustments include compensation for pulse discharge 40 noise.
  • Such adjustments are made during a time window coordinated with pulse discharge 40 events. Such temporal adjustments are made during a time window beginning with the discharge event and extending for a period of time that is determined by the user, such period of time being sufficient for ionized sample matter to be identified.
  • Calibrator 62 may include digital circuitry or a microprocessor to adjust the duration of the collection window.
  • FIG. 2C a graphical depiction of the intensity of adjusted signal value 94 over time is depicted.
  • the graphical depiction of FIG. 2C represents signal value 94 for a discharge gas 30 , but does not indicate the elevated peaks that would be associated with matter in sample gas 32 .
  • Adjusted signal value 94 is transmitted to sample and hold processor 64 , which quantifies the desired components of adjusted signal value 94 , such desired components correlating to pulsed discharges 40 and disregarding signals intermediate pulsed discharge 40 events.
  • intensity signal value 86 may not be measured, but treated as a constant signal value 86 .
  • the collected signal 92 is collected during a time window initiated in response to a pulse discharge 40 .
  • the sensitivity of the resultant measurement will be decreased as compared to the sensitivity of the preferred embodiment disclosed.
  • such alternative embodiment provides an improved measurement method over the prior art as such embodiment incorporates the advantages of modular identification of charged particles as opposed to determination of average induced current.
  • sample and hold processor 64 accumulates the total value of adjusted collected value 94 for each pulse discharge 40 . This process can also be accomplished through integration of adjusted collected value 94 .
  • Frequency signal value 84 provides a timing mechanism for signal and hold processor 64 and for calibrator 62 .
  • Frequency signal value 84 may be a digital output that comprises a series of on/off pulses with the on pulses proportional to the pulsed discharge event 40 .
  • frequency signal value 84 in the on pulse condition, triggers collection of signal 94 by signal and hold processor 64 and triggers collection of collected signal 92 by calibrator 62 . More specifically, with reference to calibrator 62 , the on pulse condition triggers start of the time window during which calibrator 62 accumulates and adjusts the collected signal 92 . Accordingly, the interval between collection events of signal 94 by signal and hold processor 64 and the interval between collection time windows of collected signal 92 by calibrator 62 vary according to the interval between pulse discharges 40 .
  • the accumulated values 96 are represented over time.
  • the graphical depiction of FIG. 2D represents signal value 96 for a discharge gas 30 , but does not indicate the elevated peaks that would be associated with sample gas 32 .
  • Such signal value 96 comprises an accumulation of peaks 93 as displayed in FIG. 2C.
  • accumulated values 96 are represented over time with the occurrence of two compounds to be measured as resultants over time with peak 95 representing one compound and peak 97 representing a second compound.
  • time periods represented in FIGS. 2A, 2B and 2 C are significantly shorter than the time periods represented in FIGS. 2D and 2E.
  • Time periods represented in FIGS. 2A, 2B and 2 C involve measurements in microseconds or milliseconds while time periods represented in FIGS. 2D and 2E involve measurements in minutes.
  • Collected signals 90 are nearly uniform when produced by pure discharge gas 30 . Initiating the detection process with discharge gas 30 and sample gas 32 (consisting of only carrier gas) develops baseline values for collected signal 90 , collected signal value 92 , adjusted signal value 94 and accumulated values 96 . Variations to these baseline values identify other sample matter (not shown) in sample gas 32 .
  • the degree of variation in collected signal 90 and resultant values indicate concentration of matter in sample gas 32 .
  • an alternative embodiment of the present invention comprises monitor 150 consisting of frequency monitor 152 and intensity monitor 154 , calibrator 162 , sample and hold processor 164 , electrometer 160 and bias voltage 166 applied to a gas sampling apparatus 100 including a sealed spark chamber 112 with a separate detector chamber 124 .
  • the construction and operation of apparatus 100 is disclosed in U.S. Pat. No. 5,528,150 issued to Stearns, et al.
  • the apparatus 100 incorporates photoemission in a carrier gas, preferably helium and krypton, from a pulsed direct current, referred to herein as pulse discharges 140 across electrodes 114 and 116 .
  • pulse discharges 140 a pulsed direct current
  • electrodes 114 and 116 comprise discharge electrode 114 and receptor electrode 116 .
  • Electrode 131 is grounded and electrode 130 is provided with a bias voltage 166 sufficient to attract desired charged particles created within sample chamber 124 .
  • a window membrane 140 is transparent to photoemission generated within the spark chamber 112 .
  • a sample gas 132 is exposed to such photoemissions through window membrane 140 .
  • Sample gas 132 enters through inlet 136 and exits through outlet 133 .
  • Photons generated by pulse discharges 140 energize the sample gas 132 and compounds therein producing free electrons from compounds in the sample gas 132 . Free electrons are identified at electrode 130 with the magnitude of electrons proportional to the concentration of the compound to be quantified.
  • the teachings of the preferred embodiment of the present invention are readily applied to the apparatus 100 .
  • Pulse discharges 140 generate a pulse signal 180 which is monitored by monitor 150 including frequency monitor 152 and intensity monitor 154 .
  • Frequency signal value 184 and intensity signal value 186 are transmitted to calibrator 162 .
  • Collected signal 190 is transmitted to electrometer 160 and collected signal value 192 is transmitted to calibrator 162 .
  • Calibrator 162 adjusts collected signal value 192 based on frequency signal value 184 and based on intensity signal value 186 , producing adjusted signal value 194 .
  • Such adjustments include compensation for pulse discharge 141 noise.
  • Such adjustments include temporal adjustments to co-ordinate signal value 192 collection time with pulse discharge 141 events.
  • Sample and hold processor 164 accumulates the total value of adjusted collected values 194 for each pulse discharge 141 . Accordingly, the apparatus 100 provides for modular determination of collected readings adjusted to minimize the effects of discharge noise.
  • a simplified alternative embodiment of the present invention eliminates the calibrator 62 and provides for timed collection of collected signal value 92 by sample and hold processor 64 .
  • the collected signal value 92 is not adjusted based on discharge signal value 82 .
  • the collected signal value 92 is still determined during a time window determined by sample and hold processor 64 circuitry or microprocessor. This alternative embodiment provides the advantages of modular collection of collected signal value 92 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

A pulsed discharge detector includes a device and method for modular measurement of ionization signals from a sample. The pulsed discharge detector includes a discharge source in a chamber, a collector spaced from the discharge source, a monitor connected to a discharge electrode, an electrometer connected to the collector, a calibrator and a sample and hold processor. The discharge electrodes include a source electrode centrally located in relation to the discharge chamber wall. The collector is centrally located in relation to the chamber wall. Discharge signals are monitored for time and intensity. Collected signals are adjusted based on the discharge intensity. Collected signals are collected during a time window based on the discharge occurrence time. Detector output is predicated on collected signals coordinated with pulsed discharges. The calibrator of the present invention adjusts the collected signals to reduce discharge noise. The sample and hold processor accumulates selected adjusted signal values to quantify sample concentrations.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • Not Applicable. [0001]
  • STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
  • Not Applicable. [0002]
  • BACKGROUND OF THE INVENTION
  • 1. Field of Invention [0003]
  • The present invention is directed to detectors for measuring concentrations of a gaseous sample, and more particularly directed toward a pulsed discharge detector that correlates collected data with the discharge and calibrates collected data to reduce effects of discharge noise. [0004]
  • 2. Related Art [0005]
  • Various forms of detectors are used to quantify constituents of a sample gas. Known detectors vary in how they make the sample detectable, arrange the necessary components of the detector, actually detect characteristics of the sample and process the detected data. [0006]
  • Pulsed discharge detectors ionize a discharge gas in a chamber to produce photons, introduce a sample gas to be tested and measure ionization currents of electrons produced from interaction of the photons with the sample gas. The ionization source of the detector is an electrical discharge in a discharge gas. The discharge gas may be a noble gas or a combination of noble gases. [0007]
  • As a test instrument, a pulsed discharge detector may be provided with a sample input gas eluted from a gas chromatograph column or other suitable source. The column effluent normally includes a carrier gas which is routinely input through the column at a specified flow rate. The column elutes the various constituents in peaks of concentration in a specific timed sequence, dependent on volatility of the sample constituents. [0008]
  • The gas chromatograph column separates compounds but does not quantify the concentrations of the compounds. Gas chromatograph detectors are connected downstream the column for quantitative analysis. By using a series of calibration gases, a fixed flow rate, and a specific stationary phase material, the gas chromatograph column can be used to separate compound types based upon the retention time. There may be any number of eluted peaks formed by the gas chromatograph column output to be quantified. [0009]
  • The ionization mechanism of a pulsed discharge detector is primarily photo-ionization wherein an electric discharge generates diatomic molecular emissions of photons. The high-energy photons in turn ionize the sample compounds in the detector chamber. When the pulsed discharge detector uses helium as the discharge gas, the photon generation process includes the following steps: [0010]
  • 1. The electrical discharge ionizes some helium atoms, He, to helium ions, He[0011] +.
  • 2. The He[0012] + ions combine with helium atoms, He, to form diatomic molecular ions, He2 +.
  • 3. Each diatomic ion, He[0013] 2 +, captures one electron, dissociating back to two helium atoms, 2 He, emitting photons in the process.
  • During step 3, a continuous photon emission arises from the molecular interaction—the transition of diatomic helium molecular ions to ground state helium. These photons have an energy level in the range of 13.5˜17.5 eV, which can ionize almost all compounds, except helium itself. Other processes of molecular interaction may also affect the electrical discharge, such as helium atomic emission and helium meta-stable generation. [0014]
  • Pulsed discharge detectors possess favorable characteristics over other gas chromatograph detectors. First, sensitivity is higher. The minimum detectable limit of gases present in a sample using a regular pulsed discharge detector in helium ionization detector mode is about 10 times lower than the minimum detectable limit identifiable using a flame ionization detector. Pulsed discharge detectors are operable to determine concentrations at the parts-per-billion level. Second, pulsed discharge detectors offer selectivity in response. Pulsed discharge detectors have a universal response when helium is used as the discharge gas. When helium is doped with another noble gas as the discharge gas, pulsed discharge detectors may have a selective response. Third, pulsed discharge detectors have a uniform response factor. Within an organic group the response factor increases linearly with the carbon number of the sample. Fourth, the pulsed discharge detector system does not require use of radioactive material. [0015]
  • Wentworth, et al. U.S. Pat. No. 5,394,091, teaches an ionization detector adapted for use in either helium ionization or electron capture mode. The detector utilizes a helium flow through a detector cell or chamber. The chamber has regions of spark discharge, sample introduction and sample detection. The helium flow is the only flowing material in the immediate region of the spark. A sample gas and/or carrier gas are injected and commingled with the helium gas downstream from the spark in the sample introduction region. Two electrodes, of which one is bias, detect the charged characteristics of the sample, the bias electrode at or upstream of the sample inlet and the other electrode downstream from the sample inlet. An electrometer measures the difference between the resulting currents. These current measurements are recorded on a timed basis. A base line current is formed as a result of impurities in the discharge or carrier gas. [0016]
  • Stearns, et al. U.S. Pat. No. 5,767,683, teaches a pulsed discharge detector having a bias voltage feedback system. The feedback system compares output from an electrometer connected to the collector electrode with a reference current using a comparison circuit. Output from the comparison circuit is input to a control circuit, which, in turn, outputs a bias voltage. The bias voltage is applied to the first bias electrode such that the electron current flow within the detector chamber remains constant for all concentrations of input sample gas. The instantaneous setting of the control circuit is used to form a second output. The magnitude of this second output is proportional to the concentration of a selected sample gas within the electron capture detector chamber and is the response signal of the disclosed electron capture detector system. Pulsed discharge detectors provide intermittent electrode discharges. A typical discharge voltage is in the range of 300 to 400 volts. A typical time interval between discharges is in a range of 100 microseconds to 800 microseconds. [0017]
  • Current pulsed discharge detectors measure, on a continuous basis, the current output of the sample gas, including readings during discharge events and including readings during the interval between pulses. [0018]
  • Sensitivity of measurement results is adversely affected by discharge variations, referred to as discharge noise. Discharge noise can be reduced by a high quality pulser and a clean discharge electrode surface, but cannot be eliminated. [0019]
  • In prior art pulsed discharge detectors, a relatively short discharge period (interval between discharges) increases the sensitivity of the measurement. However, a relatively short interval between discharges results in increased average electrode temperatures and relatively short electrode life cycle. [0020]
  • The present invention provides an improvement to the prior art by increasing sensitivity of the pulsed discharge detector by providing a device and method to measure ionization signals in the sample gas modularly at the time of the discharge event as opposed to a collected current, by a geometric configuration that enhances collection of signals and by providing a means of calibrating collected signals to account for discharge noise. [0021]
  • The present invention accordingly provides an improvement to the prior art by allowing longer pulse periods, thereby reducing power requirement of a pulsed discharge detector and providing relatively longer product life. [0022]
  • The reduced power requirements of the detector of the present invention makes the detector particularly useful as a portable detector. [0023]
  • BRIEF SUMMARY OF THE INVENTION
  • A pulsed discharge detector includes a device and method for modular measurement of ionization signals from a sample. The pulsed discharge detector includes a discharge source in a chamber, a collector spaced from the discharge source, a monitor connected to a discharge electrode, an electrometer connected to the collector, a calibrator and a sample and hold processor. The discharge electrodes include a source electrode centrally located in relation to the discharge chamber wall. The collector is centrally located in relation to the chamber wall. Discharge signals are monitored for time and intensity. Collected signals are adjusted based on the discharge intensity. Collected signals are collected during a time window based on the discharge occurrence time. Detector output is predicated on collected signals coordinated with pulsed discharges. The calibrator of the present invention adjusts the collected signals to reduce discharge noise. The sample and hold processor accumulates selected adjusted signal values to quantify sample concentrations. [0024]
  • Accordingly, the objects of this invention are to provide, among other things, a pulsed discharge detector and method of operation that: [0025]
  • adjusts the detected values for variations in intensity of the corresponding individual discharges; [0026]
  • isolates the collected ionization signal from each particular discharge; [0027]
  • integrates the resulting ionization signals from each discharge in order to establish concentration of the sample; and [0028]
  • minimizes power consumption allowing for portability of the detector. [0029]
  • Other objects of this invention will become evident throughout the reading of this application.[0030]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a cross-sectional view of a detector of the present invention, including a schematic depiction of components. [0031]
  • FIG. 2A is a graphical depiction of a monitored discharge signal overtime. [0032]
  • FIG. 2B is a graphical depiction of the collected signal overtime as in FIG. 2A. [0033]
  • FIG. 2C is a graphical depiction of the adjusted signal overtime as in FIG. 2A. [0034]
  • FIG. 2D is a graphical depiction of the output signal overtime as in FIG. 2A. [0035]
  • FIG. 2E is a graphical depiction of an output signal over time indicating concentration of sample compounds. [0036]
  • FIG. 3 is a cross-sectional view of an alternative embodiment incorporating the components of the present invention.[0037]
  • DESCRIPTION OF THE INVENTION
  • Referring to FIG. 1, [0038] detector 10 of the present invention is depicted. Detector 10 is typically integrated into an analytical system. Devices such as a gas chromatograph column (not shown) are typically used upstream of detector 10 to provide a sample gas (not shown), and other devices, such as a computer with interpretation software (not shown), are used to receive, store, manipulate and report generated data. A primary purpose of detector 10 is to determine the quantities of compounds in a sample gas.
  • [0039] Detector 10 includes closed chamber 12 within detector housing 11. In the exemplary embodiment, chamber 12 is an elongated hollow space in housing 11, oriented lengthwise along chamber axis 18. One end of chamber 12 is discharge end 14 and the other is collector end 16.
  • An [0040] electrical discharge source 20 is located proximate discharge end 14. In the exemplary embodiment, discharge source 20 includes source electrode 22 and receptor electrode 24. Source electrode 22 extends into chamber 12 proximate discharge end 14 of housing 11. Tip 42 of source electrode 22 is located at the central axis 18 of cylindrical chamber 12. In a preferred embodiment, source electrode 22 extends through discharge end 14 at the center of discharge end 14 and is arranged co-axially with the central axis 18 of chamber 12. Electrical source connection 21 is located outside housing 11 and provides an electrically conductive link of source electrode 22 to a power source (not shown). Receptor electrode 24 is emplaced circumferentially in the wall of housing 11, proximate tip 42 of source electrode 22. In a preferred embodiment, receptor electrode 24 extends circumferentially about cylindrical chamber 12. Electrical receptor connection 23 is located outside housing 11 and provides an electrically conductive link to receptor electrode 24. The configuration of tip 42 in relation to electrode 24 allows tip 42 to be equally distant from electrode 24 surfaces.
  • [0041] Collector 26 extends into chamber 12 proximate collector end 16. Collector tip 46 is located at the central axis 18 of cylindrical chamber 12. In a preferred embodiment, collector 26 extends through collector end 16 at the center of collector end 16 and is arranged co-axially with the central axis 18 of chamber 12. Accordingly, collector 26 is equally distant from chamber wall 28. Electrical collector connection 25 is located outside housing 11 and provides an electrically conductive link to collector 26.
  • In an exemplary embodiment, [0042] source electrode 22 and collector 26 are each elongated members aligned along axis 18. Collector tip 46 is spaced from source electrode tip 42.
  • [0043] Chamber 12 includes discharge region 70, expansion region 72 and collection region 74. Each of discharge region 70, expansion region 72 and collection region 74 have circular cross-sections. The diameter of the collection region 74 is greater than the diameter of discharge region 70. The diameter of expansion region 72 increases from its interface with discharge region 70 to its interface with collection region 74. Discharge region 70 extends from end 14 of chamber 12 past tip 42. Collector region 74 extends from end 16 of chamber 12 past collector tip 46.
  • A [0044] discharge gas inlet 34 is provided proximate discharge end 14 to allow the introduction of discharge gas 30 into chamber 12 at discharge region 70. Discharge gas 30 may be helium, other suitable discharge gases known in the art, or combinations thereof. Discharge gas inlet 34 connects to a pressurized supply (not shown) of discharge gas 30. In the exemplary embodiment, discharge gas inlet 34 opens into chamber 12 intermediate discharge end 14 and source electrode tip 42.
  • A [0045] sample gas inlet 36 accesses chamber 12, in expansion region 72 to provide for introduction of a sample gas 32 (not shown). Sample gas inlet 36 is connected to a source of sample gas such as a gas chromatograph column (not shown).
  • In the exemplary embodiment, [0046] sample gas 32 includes a carrier gas, typically helium, and a volume of a sample matter. The detector identifies such sample matter in sample gas 32 as variations from the carrier gas.
  • [0047] Gas vent 38 is provided at the collector end 16 of chamber 12. In the exemplary embodiment, gas vent 38 penetrates housing 11 in collector region 74 proximate collector end 16 intermediate collector tip 46 and collector end 16.
  • The [0048] chamber 12 accordingly comprises a relatively narrow discharge region 70 with discharge gas inlet 36, a conical expansion region 72 with a sample gas inlet 36 and a cylindrical collector region 74 with a gas vent 33. Collector region 74 is relatively wider than inlet region 70. Such construction enhances flow of gases within chamber 12 from end 14 toward end 16. In operation, such configuration prevents direct contact of sample gases introduced at sample gas inlet 36 with discharge source 20.
  • Electrometer [0049] 60 is attached to electrical connection 25, electrically linking electrometer 60 to collector 26. In the exemplary embodiment, a bias voltage 66 is applied to electrical connection 25 thereby providing bias voltage 66 to collector 26 and to electrometer 60.
  • Electrometer [0050] 60 is electrically connected to calibrator 62. Calibrator 62 is electrically connected to sample and hold processor 64.
  • [0051] Electrical receptor connection 23 provides an electrically conductive link from receptor electrode 24 to monitor 50, comprising frequency monitor 52 and intensity monitor 54. Frequency monitor 52 and intensity monitor 54 are each electrically connected to calibrator 62 and to sample and hold processor 64.
  • In operation, discharge [0052] gas inlet 34 is connected to a discharge gas supply line (not shown), sample gas inlet 36 is connected to a sample gas supply line (not shown) and gas vent 38 is connected to a gas vent line (not shown). The lines and detector 10 create a sealed environment. The system is then filled with a discharge gas 30 such as helium.
  • A steady flow of [0053] discharge gas 30 is introduced through discharge gas inlet 34. The discharge gas 30 flows into chamber 12 and passes through chamber 12, exiting gas vent 38. Since sample gas inlet 36 is filled and pressurized with sample gas 32, the only available flow path for discharge gas 30 is through the length of chamber 12 and then gas vent 38. The only means for any substance to enter chamber 12 is through discharge gas inlet 34 and sample gas inlet 36, and the only matter that enters chamber 12 is discharge gas 30 and sample gas 32.
  • Once [0054] discharge gas 30 is flowing through chamber 12, pulsed high voltage discharge 40 is applied to electrical connection 21 creating a spark discharge intermediate source electrode 22 and receptor electrode 24. The spacing of source electrode 22 and receptor electrode 24 and the voltage level are arranged to cause ionization of discharge gas 30 particles generating diatomic molecular emissions of photons (not shown). As the configuration of chamber 12 forces flow from inlet 34 toward vent 38, the ionized discharge gas 30 particles are conveyed toward sample gas inlet 36 and in turn ionize compounds of sample gas 32 in expansion region 72 and collector region 74.
  • Pulsed discharge [0055] 40 results in a discharge signal 80 at receptor electrode 24. FIG. 2A comprises a graphical representation of discharge signal 80 over time.
  • Although [0056] pulsed discharge 40 is designed to produce a clean, distinct and discharge signal 80 with each repetition of pulsed discharge 40, variations in intensity occur. Such variations are commonly referred to as “noise.”
  • In an exemplary embodiment, [0057] discharge signal 80 is transmitted to discharge monitor 50, comprising both frequency monitor 52 and intensity monitor 54. Frequency monitor 52 identifies synchronizing frequency signal value 84, including a discharge time and a discharge period, comprising the interval between pulsed discharges 40. Intensity monitor 54 identifies intensity signal value 86 at receptor electrode 24 for each pulsed discharge 40. Frequency signal value 84 and intensity signal value 86 may be individually or collectively transmitted to calibrator 62 and sample and hold processor 64.
  • Bias voltage [0058] 66 is applied to collector 26 through electrical connection 25. Such bias voltage 66 enhances reception of charged sample gas ions at collector tip 46. Bias voltage 66 may be positive or negative depending on the design of the detector. The amount of voltage used depends on the size of the detector.
  • [0059] Collected signal 90 is quantified by electrometer 60. Bias voltage 66 provides a measurement reference point. Bias voltage 66 variations create noise in collected signal 90. Applying bias voltage 66 directly to input lead 61 of electrometer 60, where electrical connection 25 connects with electrometer 60, minimizes such noise. Electrometer 60 produces collected signal value 92 from collected signal 90 and bias voltage 66.
  • Referring to FIG. 2B, intensity of [0060] collected signal value 92 over time is depicted. Collected signal value 92 is transmitted to calibrator 62. Calibrator 62 adjusts collected signal value 92 based on intensity signal value 86, producing adjusted signal value 94. Such adjustments include compensation for pulse discharge 40 noise.
  • In a preferred embodiment such adjustments are made during a time window coordinated with [0061] pulse discharge 40 events. Such temporal adjustments are made during a time window beginning with the discharge event and extending for a period of time that is determined by the user, such period of time being sufficient for ionized sample matter to be identified. Calibrator 62 may include digital circuitry or a microprocessor to adjust the duration of the collection window.
  • Referring to FIG. 2C, a graphical depiction of the intensity of [0062] adjusted signal value 94 over time is depicted. The graphical depiction of FIG. 2C represents signal value 94 for a discharge gas 30, but does not indicate the elevated peaks that would be associated with matter in sample gas 32. Adjusted signal value 94 is transmitted to sample and hold processor 64, which quantifies the desired components of adjusted signal value 94, such desired components correlating to pulsed discharges 40 and disregarding signals intermediate pulsed discharge 40 events.
  • In an alternative embodiment, [0063] intensity signal value 86 may not be measured, but treated as a constant signal value 86. In such alternative embodiment, the collected signal 92 is collected during a time window initiated in response to a pulse discharge 40. In such alternative embodiment, the sensitivity of the resultant measurement will be decreased as compared to the sensitivity of the preferred embodiment disclosed. However, such alternative embodiment provides an improved measurement method over the prior art as such embodiment incorporates the advantages of modular identification of charged particles as opposed to determination of average induced current.
  • In the exemplary embodiment, sample and hold [0064] processor 64 accumulates the total value of adjusted collected value 94 for each pulse discharge 40. This process can also be accomplished through integration of adjusted collected value 94.
  • [0065] Frequency signal value 84 provides a timing mechanism for signal and hold processor 64 and for calibrator 62. Frequency signal value 84 may be a digital output that comprises a series of on/off pulses with the on pulses proportional to the pulsed discharge event 40. In a preferred embodiment, frequency signal value 84, in the on pulse condition, triggers collection of signal 94 by signal and hold processor 64 and triggers collection of collected signal 92 by calibrator 62. More specifically, with reference to calibrator 62, the on pulse condition triggers start of the time window during which calibrator 62 accumulates and adjusts the collected signal 92. Accordingly, the interval between collection events of signal 94 by signal and hold processor 64 and the interval between collection time windows of collected signal 92 by calibrator 62 vary according to the interval between pulse discharges 40.
  • Referring to FIG. 2D, the accumulated [0066] values 96 are represented over time. The graphical depiction of FIG. 2D represents signal value 96 for a discharge gas 30, but does not indicate the elevated peaks that would be associated with sample gas 32. Such signal value 96 comprises an accumulation of peaks 93 as displayed in FIG. 2C.
  • Referring to FIG. 2E, accumulated [0067] values 96 are represented over time with the occurrence of two compounds to be measured as resultants over time with peak 95 representing one compound and peak 97 representing a second compound.
  • It is noted in relation to FIGS. 2A through 2E that the time periods represented in FIGS. 2A, 2B and [0068] 2C are significantly shorter than the time periods represented in FIGS. 2D and 2E. Time periods represented in FIGS. 2A, 2B and 2C involve measurements in microseconds or milliseconds while time periods represented in FIGS. 2D and 2E involve measurements in minutes.
  • Collected signals [0069] 90 are nearly uniform when produced by pure discharge gas 30. Initiating the detection process with discharge gas 30 and sample gas 32 (consisting of only carrier gas) develops baseline values for collected signal 90, collected signal value 92, adjusted signal value 94 and accumulated values 96. Variations to these baseline values identify other sample matter (not shown) in sample gas 32.
  • The degree of variation in [0070] collected signal 90 and resultant values (collected signal value 92, adjusted signal value 94 and accumulated values 96) indicate concentration of matter in sample gas 32.
  • Referring to FIG. 3, an alternative embodiment of the present invention comprises monitor [0071] 150 consisting of frequency monitor 152 and intensity monitor 154, calibrator 162, sample and hold processor 164, electrometer 160 and bias voltage 166 applied to a gas sampling apparatus 100 including a sealed spark chamber 112 with a separate detector chamber 124. The construction and operation of apparatus 100 is disclosed in U.S. Pat. No. 5,528,150 issued to Stearns, et al. The apparatus 100 incorporates photoemission in a carrier gas, preferably helium and krypton, from a pulsed direct current, referred to herein as pulse discharges 140 across electrodes 114 and 116. Referring to FIG. 3, electrodes 114 and 116 comprise discharge electrode 114 and receptor electrode 116. Electrode 131 is grounded and electrode 130 is provided with a bias voltage 166 sufficient to attract desired charged particles created within sample chamber 124. A window membrane 140 is transparent to photoemission generated within the spark chamber 112. A sample gas 132 is exposed to such photoemissions through window membrane 140. Sample gas 132 enters through inlet 136 and exits through outlet 133. Photons generated by pulse discharges 140 energize the sample gas 132 and compounds therein producing free electrons from compounds in the sample gas 132. Free electrons are identified at electrode 130 with the magnitude of electrons proportional to the concentration of the compound to be quantified. The teachings of the preferred embodiment of the present invention are readily applied to the apparatus 100. Pulse discharges 140 generate a pulse signal 180 which is monitored by monitor 150 including frequency monitor 152 and intensity monitor 154. Frequency signal value 184 and intensity signal value 186 are transmitted to calibrator 162. Collected signal 190 is transmitted to electrometer 160 and collected signal value 192 is transmitted to calibrator 162. Calibrator 162 adjusts collected signal value 192 based on frequency signal value 184 and based on intensity signal value 186, producing adjusted signal value 194. Such adjustments include compensation for pulse discharge 141 noise. Such adjustments include temporal adjustments to co-ordinate signal value 192 collection time with pulse discharge 141 events. Sample and hold processor 164 accumulates the total value of adjusted collected values 194 for each pulse discharge 141. Accordingly, the apparatus 100 provides for modular determination of collected readings adjusted to minimize the effects of discharge noise.
  • A simplified alternative embodiment of the present invention eliminates the [0072] calibrator 62 and provides for timed collection of collected signal value 92 by sample and hold processor 64. In such alternative embodiment, the collected signal value 92 is not adjusted based on discharge signal value 82. In such alternative embodiment, the collected signal value 92 is still determined during a time window determined by sample and hold processor 64 circuitry or microprocessor. This alternative embodiment provides the advantages of modular collection of collected signal value 92.
  • The foregoing disclosure and description of the invention is illustrative and explanatory thereof. Various changes in the details of the illustrated construction may be made within the scope of the appended claims without departing from the spirit of the invention. The present invention should only be limited by the following claims and their legal equivalents. [0073]

Claims (29)

What is claimed is:
1. A pulsed discharge detector having a discharge source and a collector, said detector comprising:
an electrometer;
a calibrator;
said electrometer electrically connected to said collector and to said calibrator;
a discharge monitor electrically connected to said discharge source and to said calibrator;
said electrometer detecting a collector signal;
said electrometer generating a collected signal value proportional to said collector signal;
said discharge monitor detecting a discharge signal;
said discharge monitor generating at least one discharge signal value proportional to said discharge signal; and
said calibrator receiving said at least one discharge signal value.
2. The detector as in claim 1 wherein:
said at least one discharge signal value including a discharge signal intensity value; and
said calibrator adjusting said collected signal value proportional to said discharge signal intensity value.
3. The detector as in claim 1 wherein:
said at least one discharge signal value including a discharge time value; and
said calibrator processing said collected signal value during a time window initiated in response to said discharge time value.
4. The detector as in claim 2 further comprising:
said calibrator electrically connected to a processor;
said calibrator generating an adjusted signal value proportional to said adjusted collected value; and
said processor accumulating at least one characteristic of said adjusted collected value.
5. The detector as in claim 4 wherein:
said processor electrically connected to said discharge monitor;
said processor receiving a discharge time value from said discharge monitor; and
said processor receiving said adjusted signal value during a time window initiated in response to said discharge time value.
6. The detector as in claim 1 wherein:
said collector signal comprises a measure of ions received at said collector.
7. The detector as in claim 1 further comprising:
a bias voltage generator;
said bias voltage generator electrically connected to said collector and said electrometer.
8. A pulsed discharge detector having a discharge source and a collector, said detector comprising:
an electrometer;
a processor;
said electrometer electrically connected to said collector and to said signal and hold processor;
a discharge monitor electrically connected to said discharge source and to signal and hold processor;
said electrometer detecting a collector signal;
said electrometer generating a collected signal value proportional to said collector signal;
said discharge monitor detecting a discharge signal;
said discharge monitor generating a discharge time value proportional to said discharge signal; and
said processor receiving said collected signal value during a time window initiated in response to said discharge time value.
9. The detector as in claim 8 further comprising:
a bias voltage generator;
said bias voltage generator electrically connected to said collector and said electrometer.
10. A detector for quantities of matter in a carrier gas comprising:
a closed chamber;
a discharge gas inlet, a sample gas inlet and a gas vent each accessing said closed chamber;
an electrical discharge source in said chamber;
a discharge monitor electrically monitoring said discharge source;
said discharge monitor producing a discharge signal value;
a collector within said chamber;
an electrometer electrically monitoring said collector;
said electrometer producing a collected signal value proportional ionized atoms contacting said collector;
a calibrator electrically connected to said electrometer and said discharge monitor; and
said calibrator adjusting said collected signal value for variations in said discharge signal value.
11. The detector of claim 10 further comprising:
said chamber defined by an elongated chamber wall, a discharge end and a collector end;
said chamber wall defining a cylinder at said discharge end;
said chamber wall defining a cylinder at said collector end;
said chamber having a central chamber axis;
said discharge source comprising a discharge electrode and a receptor electrode proximate said discharge end;
said discharge electrode oriented at said chamber axis;
said receptor electrode in said chamber wall proximate said discharge electrode;
said collector proximate said collector end; and
said collector oriented at said collector axis.
12. The detector of claim 11 wherein:
said discharge gas inlet accessing said chamber proximate said discharge end;
said sample inlet accessing said chamber intermediate said discharge electrode and said collector; and
said gas vent accessing said chamber proximate said collector end.
13. The detector of claim 12 wherein:
said chamber having a discharge end diameter;
said chamber having a collector end diameter; and
said collector end diameter larger than said discharge end diameter.
14. The detector of claim 13 wherein:
said chamber wall comprising a truncated conical chamber wall intermediate said discharge end and said inlet end; and
said sample inlet accessing said chamber at said truncated conical chamber wall.
15. The detector of claim 11 further comprising:
said discharge signal monitor electrically connected to said receptor electrode;
said electrometer electrically connected to said collector;
said calibrator electrically connected to said signal monitor and said electrometer; and
a processor receiving an adjusted signal value from said calibrator.
16. The detector as in claim 15 wherein:
said discharge source intermittently dischargeable;
said discharge signal monitor transmitting a discharge time signal to said processor; and
said processor receiving said adjusted signal value at a time determined in relation to said discharge time signal.
17. The detector as in claim 16 wherein:
said discharge signal monitor transmitting a discharge intensity value signal to said calibrator; and
said calibrator calibrating said collected signal proportional to said discharge intensity value signal.
18. A device for processing collected values from a pulsed discharge detector having a pulsed discharge source and a collector, comprising:
an electrometer;
a calibrator;
said electrometer electrically connected to said collector and to said calibrator;
a discharge monitor electrically connected to said discharge source and to said calibrator;
said electrometer detecting a collector signal;
said electrometer generating a collected signal value proportional to said collector signal;
said discharge monitor detecting a discharge signal;
said discharge monitor generating at least one discharge signal value proportional to said discharge signal; and
said calibrator receiving said at least one discharge signal value.
19. The device as in claim 18 wherein:
said at least one discharge signal value including a discharge signal intensity value; and
said calibrator adjusting said collected value proportional to said discharge signal intensity value.
20. The device as in claim 18 wherein:
said at least one discharge signal value including a discharge time value; and
said calibrator processing said collected signal value during a time window initiated in response to said discharge time value.
21. The device as in claim 19 further comprising:
said calibrator electrically connected to a processor;
said calibrator generating an adjusted signal value proportional to said adjusted collected value; and
said processor accumulating at least one characteristic of said adjusted collected value.
22. The device as in claim 21 wherein:
said processor electrically connected to said discharge monitor;
said processor receiving a discharge time value from said discharge monitor; and
said processor receiving said adjusted signal value during a time window initiated in response to said discharge time value.
23. The device as in claim 22 further comprising:
a bias voltage generator;
said bias voltage generator electrically connected to said collector and said electrometer.
24. A method for processing collected signals from a pulsed discharge detector having a pulse discharge source and a collector, comprising:
monitoring a pulse discharge intensity value;
determining a value of electrons impinging a collector of said detector during a determined time period; and
adjusting said collected value based on at least one discharge intensity value.
25. The method as in claim 24 further comprising:
monitoring a pulse discharge time value; and
adjusting said collected value during a time window determined in relation to said pulse discharge time value.
26. The method as in claim 25 further comprising:
transmitting selected characteristics of said adjusted collected value to a processor during a time period determined in relation to said discharge time value.
27. A method for measuring a characteristic of a sample gas comprising:
flowing a discharge gas through a closed chamber;
producing photons from said discharge gas by exposing said discharge gas to a plurality of discharges;
monitoring a discharge value of each said plurality of discharges;
introducing a sample gas into the flow of said discharge gas and said photons in said chamber to ionize at least part of said sample gas;
measuring a quantity of ions produced in said sample gas from each said plurality of discharges; and
adjusting each said measured quantity of ions based on each said discharge value.
28. The method as in claim 27 further comprising:
monitoring an occurrence time of each said discharge; and
adjusting each said measured quantity of ions during a time window determined in relation to each said discharge occurrence time.
29. The method as in claim 28 further comprising:
collecting a selected characteristic of each said adjusted measured quantity of ions during a time window determined in relation to each said discharge occurrence time.
US10/387,011 2003-03-11 2003-03-11 Gas detector with modular detection and discharge source calibration Expired - Lifetime US6842008B2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US10/387,011 US6842008B2 (en) 2003-03-11 2003-03-11 Gas detector with modular detection and discharge source calibration
EP04737310A EP1611437B8 (en) 2003-03-11 2004-03-08 Gas detector with modular detection and discharge source calibration
DE602004024182T DE602004024182D1 (en) 2003-03-11 2004-03-08 GAS DETECTOR WITH MODULAR DETECTION AND DISCHARGE SOURCE CALIBRATION
PCT/US2004/006981 WO2004081523A2 (en) 2003-03-11 2004-03-08 Gas detector with modular detection and discharge source calibration
JP2005518597A JP2007524803A (en) 2003-03-11 2004-03-08 Gas detector with module detection and discharge calibration
CN2004800064690A CN101027550B (en) 2003-03-11 2004-03-08 Gas detector with modular detection and discharge source calibration

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/387,011 US6842008B2 (en) 2003-03-11 2003-03-11 Gas detector with modular detection and discharge source calibration

Publications (2)

Publication Number Publication Date
US20040178800A1 true US20040178800A1 (en) 2004-09-16
US6842008B2 US6842008B2 (en) 2005-01-11

Family

ID=32961798

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/387,011 Expired - Lifetime US6842008B2 (en) 2003-03-11 2003-03-11 Gas detector with modular detection and discharge source calibration

Country Status (6)

Country Link
US (1) US6842008B2 (en)
EP (1) EP1611437B8 (en)
JP (1) JP2007524803A (en)
CN (1) CN101027550B (en)
DE (1) DE602004024182D1 (en)
WO (1) WO2004081523A2 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110018546A1 (en) * 2008-03-25 2011-01-27 Osaka University Discharge Ionization Current Detector
US20110187379A1 (en) * 2010-02-01 2011-08-04 Shimadzu Corporation Discharge Ionization Current Detector
CN102333411A (en) * 2011-09-19 2012-01-25 大连海事大学 Partitioned energizing atmospheric-pressure non-equilibrium plasma generator
JP2013003070A (en) * 2011-06-21 2013-01-07 Shimadzu Corp Discharge ionization current detector and gas chromatograph
WO2014078230A1 (en) * 2012-11-13 2014-05-22 Valco Instruments Company, L.P. Photoionization detector for gas chromatography having two separately ionizing sources
US9188570B2 (en) 2012-11-13 2015-11-17 Valco Instruments Company, L.P. Photo ionization detector for gas chromatography having at least two separately ionizing sources

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5470543B2 (en) 2010-04-26 2014-04-16 株式会社島津製作所 Discharge ionization current detector
JP5704065B2 (en) * 2011-12-16 2015-04-22 株式会社島津製作所 Discharge ionization current detector
US8963554B2 (en) 2012-08-23 2015-02-24 Valco Instruments Company, L.P. Pulsed discharge helium ionization detector with multiple combined bias/collecting electrodes for gas chromatography and method of use
RU2705194C1 (en) * 2019-03-13 2019-11-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технический университет им. А.Н. Туполева-КАИ" (КНИТУ-КАИ) Device for measuring concentration of ions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5394091A (en) * 1991-02-28 1995-02-28 Wentworth; Wayne E. System for detecting compounds in a gaseous sample by measuring photoionization and electron capture induced by spark excitation of helium
US5602468A (en) * 1995-08-07 1997-02-11 Radcal Corporation Method and apparatus for ion chamber identification
US5767683A (en) * 1996-07-26 1998-06-16 Stearns; Stanley D. System for detecting compounds in a gaseous sample using photoionization, electron capture detection, and a constant current feedback control circuit which responds to compound concentration
US6448777B1 (en) * 2001-08-20 2002-09-10 Agilent Technologies, Inc. Hermetically-sealed miniaturized discharge ionization detector
US6509562B1 (en) * 1999-09-16 2003-01-21 Rae Systems, Inc. Selective photo-ionization detector using ion mobility spectrometry

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634754A (en) * 1969-06-23 1972-01-11 Shell Oil Co Method and apparatus for linearly measuring electron capture with an electron capture detector
DE4038994C2 (en) * 1990-12-06 1994-03-10 Lehmann Martin Method for determining a measured variable and measuring arrangement
US5294794A (en) * 1993-02-18 1994-03-15 Thermo King Corporation Automatic compensation for ion mobility sensor
JP3718971B2 (en) * 1997-09-19 2005-11-24 株式会社島津製作所 Mass spectrometer
CA2379892A1 (en) * 1999-07-29 2001-02-08 David Systems & Technology S.L. Plasma converter of fossil fuels into hydrogen-rich gas

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5394091A (en) * 1991-02-28 1995-02-28 Wentworth; Wayne E. System for detecting compounds in a gaseous sample by measuring photoionization and electron capture induced by spark excitation of helium
US5602468A (en) * 1995-08-07 1997-02-11 Radcal Corporation Method and apparatus for ion chamber identification
US5767683A (en) * 1996-07-26 1998-06-16 Stearns; Stanley D. System for detecting compounds in a gaseous sample using photoionization, electron capture detection, and a constant current feedback control circuit which responds to compound concentration
US6509562B1 (en) * 1999-09-16 2003-01-21 Rae Systems, Inc. Selective photo-ionization detector using ion mobility spectrometry
US6448777B1 (en) * 2001-08-20 2002-09-10 Agilent Technologies, Inc. Hermetically-sealed miniaturized discharge ionization detector

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110018546A1 (en) * 2008-03-25 2011-01-27 Osaka University Discharge Ionization Current Detector
US8421470B2 (en) 2008-03-25 2013-04-16 Osaka University Discharge ionization current detector
US20110187379A1 (en) * 2010-02-01 2011-08-04 Shimadzu Corporation Discharge Ionization Current Detector
US8970221B2 (en) * 2010-02-01 2015-03-03 Shimadzu Corporation Discharge ionization current detector
JP2013003070A (en) * 2011-06-21 2013-01-07 Shimadzu Corp Discharge ionization current detector and gas chromatograph
CN102333411A (en) * 2011-09-19 2012-01-25 大连海事大学 Partitioned energizing atmospheric-pressure non-equilibrium plasma generator
WO2014078230A1 (en) * 2012-11-13 2014-05-22 Valco Instruments Company, L.P. Photoionization detector for gas chromatography having two separately ionizing sources
US8829914B2 (en) 2012-11-13 2014-09-09 Valco Instruments Company, L.P. Photo ionization detector for gas chromatography having two separately ionizing sources and methods of use
KR101542720B1 (en) 2012-11-13 2015-08-06 발코 인스트루먼츠 컴퍼니, 엘피 Photoionization detector for gas chromatography having two separately ionizing sources
US9188570B2 (en) 2012-11-13 2015-11-17 Valco Instruments Company, L.P. Photo ionization detector for gas chromatography having at least two separately ionizing sources

Also Published As

Publication number Publication date
EP1611437A2 (en) 2006-01-04
CN101027550A (en) 2007-08-29
WO2004081523A3 (en) 2005-02-10
EP1611437B1 (en) 2009-11-18
EP1611437A4 (en) 2008-02-27
US6842008B2 (en) 2005-01-11
DE602004024182D1 (en) 2009-12-31
WO2004081523A2 (en) 2004-09-23
CN101027550B (en) 2010-12-01
EP1611437B8 (en) 2010-02-17
JP2007524803A (en) 2007-08-30

Similar Documents

Publication Publication Date Title
US5394092A (en) System for identifying and quantifying selected constituents of gas samples using selective photoionization
US5153519A (en) High voltage spark excitation and ionization detector system
US5541519A (en) Photoionization detector incorporating a dopant and carrier gas flow
US5394091A (en) System for detecting compounds in a gaseous sample by measuring photoionization and electron capture induced by spark excitation of helium
US7812614B2 (en) Electron capture detector and nonradiative electron capture detector
US6842008B2 (en) Gas detector with modular detection and discharge source calibration
US5594346A (en) Apparatus and methods for identifying and quantifying compounds using a plurality of pulsed rare gas photoionization detectors
US20150369777A1 (en) Discharge ionization current detector and tuning method for the same
US6457347B1 (en) Glow discharge detector
US5528150A (en) Gas sampling apparatus including a sealed chamber cooperative with a separate detector chamber
EP0745846B1 (en) Improved pulsed discharge systems
US5532599A (en) High voltage spark excitation and ionization system including disc detector
CA2213975C (en) Improved system for detecting compounds in a gaseous sample using induced photoionization for electron capture detection
US9513257B2 (en) Discharge ionization current detector and method for aging treatment of the same
US3318149A (en) Gas chromatography system
JP3279561B2 (en) High voltage spark excitation and ionization detection system
US8188442B2 (en) Non-radioactive electron capture detector for GC
US6606899B1 (en) Total impurity monitor for gases
US6107805A (en) Extended detection zone in an ionization detector
US6736000B2 (en) Stable glow discharge detector
US4680472A (en) Process and apparatus for the stabilization of measuring results furnished by an "electron capture" detector with identification of anomalies affecting the detector
Anikhindi et al. The Analysis of Current Pulses Occurring in Ozonizer Discharges Excited by Alternating Voltages
RU2093916C1 (en) Method for gas investigation
SU1153280A1 (en) Discharge detector for gas chromatography
Koo et al. Glow discharge detector

Legal Events

Date Code Title Description
AS Assignment

Owner name: VALCO INSTRUMENTS CO., INC., TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CAI, HUAMIN;REEL/FRAME:015372/0251

Effective date: 20041013

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: VALCO INSTRUMENTS CO., L.P.,TEXAS

Free format text: CONVERSION OF CORPORATE ENTITY;ASSIGNOR:VALCO INSTRUMENTS CO., INC.;REEL/FRAME:024320/0129

Effective date: 20051229

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: VALCO INSTRUMENTS COMPANY, INC., TEXAS

Free format text: CONVERSION OF CORPORATE ENTITY;ASSIGNOR:VALCO INSTRUMENTS COMPANY, L.P.;REEL/FRAME:059232/0008

Effective date: 20181030

FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY